Single bath fungicidal chrome-zirconyl acetate mineral dyeing process for cellulosics

ABSTRACT

The present unique process is based on an acid complex of chromium hydroxydiacetate and zirconyl acetate and a dodecylbenzylfurfuryldimethyl ammonium chloride quaternary, with or without an aliphatic polyether wetting agent. The clear blackish-green bath is stable for days, and decomposes on cellulosics, with heat, to produce a chrome gray-green mineral dyeing along with a quaternary-zirconium fungicide. The process makes it possible to produce a chrome fungicidal mineral dyeing from a single bath zirconyl acetate system, where no alkali is required, and only one bath is required to deposit both dye and fungicide.

United States Patent 1 Conner Nov. 4, 1975 [75] lnventorz Charles J.Conner, Metairie, La.

[73] Assignee: The United States of America as represented by theSecretary of Agriculture, Washington, DC.

[22] Filed: Mar. 22, 1974 [21] Appl. No.: 453,910

[52] US. Cl. 8/52; 8/99; 8/115.6; 117/1385; 252/8.8

[51] Int. Cl. C09B 63/00; D06P 3/64 [58] Field of Search .1 8/52, 99,115.6

[56] References Cited UNITED STATES PATENTS 1,648,433 11/1927 White 8/173,169,043 2/1965 Baumgartner 8/4 3,423,162 1/1969 Papayannis et a1.8/94.25

FOREIGN PATENTS OR APPLICATlONS 778,415 7/1957 United Kingdom OTHERPUBLICATIONS Conner et al., Textile Research Journal, 1967, 37, pp.94-102.

Conner et al., Textile Research Journal, 1964, 34, pp. 347-357.

Zorn et al., Das Leder, 1965, 16, pp. 73-78.

Primary Examiner-Joseph L. Schofer Assistant ExaminerA. L. ClingmanAttorney, Agent, or Firm-M. Howard Silverstein; Max D. Hensley [57]ABSTRACT The present unique process is based on an acid complex ofchromium hydroxydiacetate and zirconyl acetate and adodecylbenzylfurfuryldimethyl ammonium chloride quaternary, with orwithout an aliphatic polyether wetting agent. The clear blackish-greenbath is stable for days, and decomposes on cellulosics, with heat, toproduce a chrome gray-green mineral dyeing along with aquaternary-zirconium fungicide. The process makes it possible to producea chrome fungicidal mineral dyeing from a single bath zirconyl acetatesystem, where no alkali is required, and only one bath is required todeposit both dye and fungicide.

6*Claims, N0 Drawings 1 SINGLE BATH FUNGIC IDAL CHROME-ZIRCONYL ACETATEMINERAL DYEING PROCESS FOR CELLULOSICS The prior art discloses manymineral dyeing processes based on' two or more bathsto produce greenchromium oxide deposits (dye pigments) in cellulosics. These processesare resultant from the decomposition of a chromium acid salt, withalkalis. Several other single bath dye processes are known, but theseare based on alkaline chromium salt complexes. These alkaline systemsrequire a Zirconyl ammonium carbonate complex of a trivalent orhexavalent chromium salt in a strongly alkaline system, and thesesystems are imcompatible with acid p systems, such as the presentinventlon.

It has been known from prior art that trivalent chromium salts reactwith alkali hydroxides and carbonates to produce a precipitate ofhydrated chromium oxide, having a gray-green color, and referred to inthe trade as pearl gray. The cellulosic is wetted with a solution of thetrivalent chrmoium salt in water, oven dried, and then wetted in asecond alkali bath to precipate the hy drated chromium oxide (mirieral'dye). The prior art A third object of the invention is to demonstratethe feasibility of locking both the'chromium ion and the quaternary(through the furfuryl radical) to cellulosics. with basic Zirconylacetate. to produce a unique chrome fungicidal mineral dyeing by asimple pad. dry. and cure technique.

The prior art teaches that conventional chromic chloride will degradeand tender cellulosics when heat dried on them. Chromiumhydroxydiacetate, with zirconyl acetate. anddedecylbenzylfurfuryldimethyl ammonium chloride, is slightly acid fromacetic acid. but does not degrade or tender the cellulosic, even withtemperatures as high as 155C.

Utility of the invention is obviously in the field of textile mineraldyeings and weatherable goods. such as for tents. sails. tarpaulins,umbrellas, awnings. rope. shoe the invention and certain aspects of itsusefulness.

also teaches that this wet treatedfabric (or cellulosic) The presentinvention consists of preparing a solution of chromium hydroxydiac etateinwater, adding zirconyl acetate, and dodecylbenzylfurfuryldimethylammonium chloride (quaternary),v to produce a clear blackish-green bathsolution. To increase wettability of cellulosics, anda deeper. colorshade, a small amount of aliphatic polyester (wetting agent) isincorporated into the bath. The. bath is stable for days inan opencontainer. In use, the cellulosic is wetted with the bath, squeezed freeof excess liquid, and then oven dried at temperature between 120 and130C for 2 or 3 minutes, followed by oven cur ing at 150C to 155C for 2or 3 minutes. The cured dyed cellulosic is dyed a green-gray. Thezirconyl acetate is converted to basic zirconyl acetate during heatcuring, producingan insoluble complex deposit with the chromium hydroxydiacetate and the furfuryl quaternary. The dyed cellulosic is washed for1 to 2 minutes in hot tap water, squeezed free of excess water, and ovendried at 130C to 135C for 2 to 3 minutes. The cellulosic is permanentlymineral dyed a green-gray color and contains the quaternary-basiczirconyl acetate fungicide.

The main object of the invention is to provide a single-bath chromemineral dye bath with fungicide, having an acid (acetic) p, and beingcapable of depositing a chrome mineral dyeing and fungicide through heatdecomposition onto cellulosics, using a simple pad, dry, cure technique,followed by water washing and drying. The grayish-green color shade, soproduced, conforms with a true pearl gray, and is desired in the trade.

to produce fungicidal chrome mineral dyeings, where the fungicide iscolorless and does not affect the color shade.

These are not to be interpreted as limiting the invention in any mannerwhatever. The treatments were also ap* plied to paper. porous ceramics.wood, and other fabrics having a cellulose composition.

EXAMPLE 1 Five (5.0) grams of 50% syrupy chromium hydroxydiacetate weremixed with 25 grams of distilled water. and stirred until a clearuniform blackish-green solution was produced(A).

In another 250 ml beaker, five (5.0) grams of 50% syrupy chromiumhydroxydiacetate, 10.0 grams of 50% zirconyl acetate solution. and 15.0grams of distilled water were mixed and stirred to a clearblackish-green solution( B).

Two pieces of scoured 9 02. cotton duck. 5 X 4 inches. were cut. Onepiece was wetted in (A) and the other in (B). The wetted duck sampleswere blotted free of excess liquid. oven dried at 120C/2 minutes. andoven cured at 1 50C/2 minutes. The cured samples were washed with hottap water for 2 minutes. The duck sample treated with (A), withoutzirconyl acetate. lost all of the green color (deposit from curing) inwashing. The duck sample treated with (B), with zirconylacetatearetained a gray-green mineral dye deposit after washing, showingthat zirconyl acetate locks the chromium ion to cellulosic fabric.

EXAMPLE 2 Zirconyl acetate produces an insoluble fungicide deposit withquaternary compounds containing unsaturated alkyl radicals, such asfurfuryl, making it possible to deposit a colorless fungicide intocellulosics, when the quaternary has a microbiological activity. Thefollowing furfuryV quatemary was used to demonstrate this:

I Dodecylbenzyl furfuryl dimethyl ammonium ]chloride (quaternary)fur-fury quater- 4 nary" 0"" w This quaternary contains an unsaturatedfurfuryl alkyl radical, which is subject to reaction and lock-on to thecellulosic with zirconyl acetate, when heat curing deposits thequaternary with basic zirconyl acetate. The reactions could proceed asfollows:

basic zirconyl acetate virconyl acetate and the basic acetate quaternarydeposit would have the following lock-on structure:

In order to demonstrate this. grams of the furfuryl quaternary, grams of13% ZrO- zirconyl acetate. and 30 grams of water were mixed to grams ofclear solution. A section of scoured 9 oz. cellulosic cotton duck waswetted with the solution. blotted free of excess, and oven dried at C/2minutes, followed by oven curing at C for 2 minutes. The fabric had ayellowish-white color, and was hot tap water washed for 2 minutes.followed by oven drying at 120C/2 minutes. The washed and dried fabricretained a nitrogen content, as evidenced by decomposition of theresidue and estimation as ammonia.

paper. until thoroughly extracted. The solid residue was dried anddigested with concentrated sulphuric acid. followed by treatment withsodium hydroxide. Ammonia was liberated. showing the presence ofnitrogen (quaternary) in the washed basic zirconyl acetate residue.

EXAMPLE 3 The following bath formulation demonstrates the compatibilityof the chromium hydroxydiacetate with the zirconylacetate and furfurylquaternary:

Approx.-l5q- 5.00 grams chromium hydroxydiacetate (50% syrup)Appro.\.--102l5.00 grams zirconyl acetate (50% solution) Approx.--10'/10.00 grams distilled water Approx. SQ- 2.00 grams "Furfuryl quaternary"Approx.-l0l).' -3l00 grams Dye-Fungicide Bath (Blackish-green color)EXAMPLE 4 The fungicidal dyeing of greige cotton duck was made feasibleby the incorporation of a wetting agent into the dye bath, and alsoreducing the bath concentration (which would reduce chemical costs):

Approx. 8.0% 2.50 grams chromium hydroxydiacetate (5071 syrup) Approx.25.09? 8.00 grams zirconyl acetate (50% solution) Approx. 56.0% l 8.00grams distilled water Approx. 5.0% 1.50 grams Furfuryl quaternaryApprox. 6.0% 2.00 grams wetting agent (Discopen 205) (aliphaticpolyester mfg. by Dixie Size 6'; Chemical Co. of Columbus. Ga.) Approx.l00.0/l --32.()() grams Wettable Dye-Fungicide Bath Some of the bath wasevaporated to dryness on the hot plate, producing a solid glassyresidue. This was pulverized, washed with warm distilled water on afilter (Blackish-Green) The clear blackish-green bath was stable for 96hours in an open beaker, and possibly indefinitely in closed containers.

A section of 6 X 4 inches scoured duck was wetted with the bath,squeezed free of excess liquid, dried at 120C/3 minutes, followed byoven curing at 155C/2 minutes. The duck was dyed a deep shade ofgreenishgray. It was hot tap water washed (55C for 2 minutes. followedby oven drying at 120C-l 30C for 2 minutes. The dyed, washed, and driedduck was uniformly dyed a greenish-gray color shade of good depth ofcolor, and comparable to conventional pearl grays on the market.

EXAMPLE 5 Samples of scoured duck, 6 X 4 inches, dyed with the bath andprocedures of Examples 1, 3 and 4 were selected. The dyed, washed, anddried ducks were wetted in a paraffinammonium stearate water waxemulsion containing 7% paraffin and 2 to 3% of ammonium stearateemulsifier. The wetted samples were blotted free of excess liquid, ovendried at 130C for 3 minutes, and oven cured at 150C for 2 minutes. Thewax finisheddyed samples were greenish-gray in color, and waterrepellent. Spray ratings were recorded of 90 to 100, showing a wax waterrepellent to attribute hydrophobic characteristics without adverselyaffecting the color. The paraffin-ammonium stearate emulsion is acommercial product, manufactured by Blue Grass Resins Inc. ofLouisville, Ky. under the name Blu Wax".

EXAMPLE 6 Untreated 9 oz. scoured duck, and 9 oz. scoured duck, dyed bythe bath and procedures in Example 4. were subjected to Scott BreakingStrength determinations. The untreated duck had a breaking strength of132 lbs., while the dyed duck had a breaking strength of 130 lbs.,showing that the fungicidal dye treatment does not degrade fabricstrength significantly.

EXAMPLE 7 The dodecylbenzyl dimethyl furfuryl ammonium chloridequaternary was tested for Phenol Coefficient. and was found to have aPhenol Coefficient of 125. This is indicative of a high microbiologicalactivity. Since Example 2 demonstrates that this compound can be lockedonto cellulosic materials with zirconyl acetate, by heat conversion to abasic zirconyl acetate derivative, it follows that this deposit wouldhave microbiological activity.

EXAMPLE 8 A soil burial test was conducted with plain untreated scoured9 oz. duck and scoured 9 oz. duck which had been fungicidally dyed withthe bath and by the procedures in Example 4. The untreated scoured duckcontrol rotted completely in 1 week, while the fungicidally dyed ducksample resisted 3 weeks in soil burial, showing the treatment to affordmicrobiological protection to the 9 oz. duck.

EXAMPLE 9 The stability of the dye bath in Example 4 was evalu ated byallowing the bath to stand in a beaker at room temperature (25C) forseveral days. The bath remained stable and clear for 5 days. A sample ofscoured duck was wetted with the 5-day old bath, blotted free of excessliquid, dried at 130C/2 minutes and oven cured at 150C/3 minutes. Theduck was uniformly dyed a greenish-gray, resisted a hot tap water washfor l minute, and after drying at 130C for 3 minutes, was found 6 to bedyed a deep greenish-gray, comparable to dyeings obtained with a freshlyprepared bath (per Example 4).

EXAMPLE 10 The dodecylbenzyl furfuryl dimethyl ammonium chloridequaternary not only functionsas a fungicide. but also produces a deeperchrome mineral dye color shade, thus making it an essential processcomponent for the dyeing as well as the fungicidal effects. This isdemonstrated by preparing two separate, baths, one without thequaternary, and one with the quaternary, and dyeing separate scouredduck samples with each of the baths:

Bath A (Without Quatemary) 5.0 grams Chromium Hydroxydiacetate (50%Syrup- Diamond Alkali Co.) 15.0 grams 50% Zirconyl Acetate Solution(Harshaw Chemical Co.) 10.0 grams Distilled Water 30.0 grams Dye Bath AA second bath (B) was prepared similar to bath (A). but including thedodecylbenzyl furfuryl dimethyl ammonium chloride quaternary:

Bath B1 (With Quaternary) 5.0 grams Chromium Hydroxydiacetate (50%Syrup- Diamond Alkali Co.) 15.0 grams 50% Zirconyl Acetate Solution(Harshaw Chemical Co.) 10.0 grams Distilled Water 2.0 grams Quaternary32.0 grams Dye Bath B A piece of scoured duck (5 X 4 inches) was wettedin Bath A, blotted, and oven dried and cured according to Example 3procedures. A piece of scoured duck was wetted in Bath B, blotted, andoven dried and cured according to Example 3 procedures. The cured ducksamples were hot tap water washed for two minutes, followed by ovendrying at C/2 minutes.

The duck sample dyed with Bath A, without quaternary, was dyed a lightshade of greenish'gray. while the duck sample dyed with Bath B was dyeda deep greenish-gray color shade, showing the quaternary to be essentialto deposit of maximum dye pigment, as well as to furnish a fungicidaleffect with the mineral dyeing. Both the chromium ion and the quaternaryare well locked to the cotton duck, together. to produce a fungicidalchrome mineral dyeing on the cellulosic.

I claim:

1. A single bath chrome mineral dyeing process for cellulosics (fabrics)comprising:

a. Wetting a cellulosic material in an aqueous solution containing about1 to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to25 weight percent zirconyl acetate, and about 72.5 to 83 weight percentwater,

b. drying, and subsequently curing the wetted fabric from (a).

2. A fungicidal single bath chrome mineral dyeing process forcellulosics (fabrics) comprising:

a. Wetting a cellulosic material in an aqueous solution containing about1 to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to25 weight percent zirconyl acetate, 4 to,6 weight per- 7 centdodecylbenzylfurfuryldimethyl ammonium chloride (quaternary), and theremainder water to make 100 weight percent.

b. drying. and subsequently curing the wetted fabric from (a).

3. A fungicidal single bath chrome mineral dyeing process forcellulosics (fabrics) comprising:

a Wetting a cellulosic material in an aqueous solution containing aboutI to 2.5 weight percent chromium (as chromium hydroxydiacetate). l6'to25 weight percent zirconyl acetate. 4 to 6 weight percentdodecylbenzylfurfuryldimethyl ammonium chloride. and about 5 to 6 weightpercent of an aliphatic polyether. with the difference as water to make100 weight percent.

b. drying and subsequently euring the wetted fabric from (a).

4. A fungicidal single bath chrome mineral dyeing process forcellulosics (fabrics) comprisingr a. Wetting a cellulosic material in anaqueous solution containing about 1 to 2.5 weight percent chromium (aschromium hydroxydiacetate). 16 to weight percent zirconyl acetate. 4 to6 weight percent dodecylbenzylfurfuryldimethyl ammonium chloride, andthe remainder as water to make 100 weight percent.

b. drying. and subsequently curing the wetted fabric from (a). and

c. wetting the dyed cellulosic from (b) with a paraffin-ammoniumstearate water-wax emulsion. containing 77! paraffin (weight percent).and

d. drying and subsequently curing the wetted fabric from (c).

5. A fungicidal signle bath chrome mineral dyeing process forcellulosics (fabrics) comprising:

a. Wetting a cellulosic material in an aqueous solution containing aboutI to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to25 weight percent zirconyl acetate. 4 to 6. weight percentdodecylbenzylfurfuryldimethyl ammonium chloride. and about 5 to 6 weightpercent of an aliphatic'polyether (wetting agent). with the differenceas water to make weight percent.

b. drying and subsequently curing the wetted fabric from (a). and c.wetting the dyed fabric from (b) with a paraffinammonium stearatewater-wax emulsion, containing 7% paraffin (weight percent). and

d. drying and subsequently curing the wetted fabric from (c). 7

6. A single bath chrome mineral dyeing process fo cellulosics (fabrics)comprising:

a. Wetting a cellulosic material in an aqueous solution containing about1 to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to25 weight percent zireonyl acetate, and the difference (about 72.5 to 83weight percent) water to make 100 weight percent.

b. drying and subsequently curing the wetted fabric from (a). and

c. wetting the dyed cellulosic from (b) with a paraffin-ammoniumstearate water-wax emulsion, containing 7% paraffin (weight percent).and

d. drying and subsequently curing the wetted fabric

1. A single bath chrome mineral dyeing process for cellulosics (fabrics)comprising: a. Wetting a cellulosic material in an aqueous solutioncontaining about 1 to 2.5 weight percent chromium (as chromiumhydroxydiacetate), 16 to 25 weight percent zirconyl acetate, and about72.5 to 83 weight percent water, b. drying, and subsequently curing thewetted fabric from (a).
 2. A fungicidal single bath chrome mineraldyeing process for cellulosics (fabrics) comprising: a. Wetting acellulosic material in an aqueous solution containing about 1 to 2.5weight percent chromium (as chromium hydroxydiacetate), 16 to 25 weightpercent zirconyl acetate, 4 to 6 weight percentdodecylbenzylfurfuryldimethyl ammonium chloride (quaternary), and theremainder water to make 100 weight percent, b. drying, and subsequentlycuring the wetted fabric from (a).
 3. A fungicidal single bath chromemineral dyeing process for cellulosics (fabrics) comprising: a. Wettinga cellulosic material in an aqueous solution containing about 1 to 2.5weight percent chromium (as chromium hydroxydiacetate), 16 to 25 weightpercent zirconyl acetate, 4 to 6 weight percentdodecylbenzylfurfuryldimethyl ammonium chloride, and about 5 to 6 weightpercent of an aliphatic polyether, with the difference as water to make100 weight percent, b. drying and subsequently curing the wetted fabricfrom (a).
 4. A fungicidal single bath chrome mineral dyeing process forcellulosics (fabrics) comprising: a. Wetting a cellulosic material in anaqueous solution containing abOut 1 to 2.5 weight percent chromium (aschromium hydroxydiacetate), 16 to 25 weight percent zirconyl acetate, 4to 6 weight percent dodecylbenzylfurfuryldimethyl ammonium chloride, andthe remainder as water to make 100 weight percent, b. drying, andsubsequently curing the wetted fabric from (a), and c. wetting the dyedcellulosic from (b) with a paraffin-ammonium stearate water-waxemulsion, containing 7% paraffin (weight percent), and d. drying andsubsequently curing the wetted fabric from (c).
 5. A fungicidal signlebath chrome mineral dyeing process for cellulosics (fabrics) comprising:a. Wetting a cellulosic material in an aqueous solution containing about1 to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to25 weight percent zirconyl acetate, 4 to 6 weight percentdodecylbenzylfurfuryldimethyl ammonium chloride, and about 5 to 6 weightpercent of an aliphatic polyether (wetting agent), with the differenceas water to make 100 weight percent, b. drying and subsequently curingthe wetted fabric from (a), and c. wetting the dyed fabric from (b) witha paraffinammonium stearate water-wax emulsion, containing 7% paraffin(weight percent), and d. drying and subsequently curing the wettedfabric from (c).
 6. A SINGLE BATH CHROME MINERAL DYEING PROCESS FORCELLULOSICS (FABRICS) COMPRISING: A. WETTING A CELLULOSIC MATERIAL IN ANAQUEOUS SOLUTION CONTAINING ABOUT 1 TO 2.5 WEIGHT PERCENT CHROMIUM (ASCHROMIUM HYDROXYDIACETATE), 16 TO 25 WEIGHT PERCENT ZIRCONYL ACETATE,AND THE DIFFERENCE (ABOUT 72.5 TO 83 WEIGHT PERCENT) - WATER TO MAKE 100WEIGHT PERCENT, B. DRYING AND SUBSEQUENTLY CURING THE WETTED FABRIC FROM(A) AND C. WETTING THE DYED CELLULOSIC FROM (B) WITH A PARAFFINAMMONIUMSTEARATE WATER-WAX EMULSION, CONTAINING 7% PARAFFIN (WEIGHT PERCENT),AND D. DRYING AND SUBSEQUENTLY CURING THE WETTED FABRIC FROM (C).